Keratinaceous fiber dye of hydroquinone and either dihydroxyphenylalanine or dihydroxyphenylglycine and method of its use



KERATINA'CEOUS FIBER DYE OF HYDROQUI- NONE AND EITHERDIHYDROXYPHENYLALA- NINE OR DIHYDROXYPHENYLGLYCINE AND METHOD OF ITS USEPhilip F. Rosmarin, New York, N. Y., and Myron Pantzer, Englewood, N.J., assiguors to Apod Corporation, New York, N. Y., a corporation of NewYork No Drawing. Application August 20, 1957 Serial No. 679,129

19 Claims. (Cl. 132-7) This invention is that of reactant-dyecompositions derived from reaction, under alkaline conditions, betweenhydroquinone and a dihydroxyphenylalanine, particularly3,4-dihydroxyphenylalanine, and/or a dihydroxyphenylglycine,particularly 3,4-dihydroxyphenylglycine.

The invention also includes the preparation of these reactant-dyecompositions as well as the method of dyeing keratinaceous substancessuch as hair (growing or shorn), wool and furs with the oxidation,especially the fresh oxidation, products of these compositions, yieldingdyeings fast to light and washing.

The dye compositions of this invention are called reactant-dye. because,in dyeing the keratinaceous materials with them, the indications arethat there apparently occurs some kind of reaction between the materialsand the dyeing solution composition rather than a mere surface coloring.

By fresh oxidation product is meant that composition containing thereaction product between the hydroxyphenylalanine and/or thedihydroxyphenylglyc'ine and the hydroquinone promptly after adding anoxidizing agent to the product, i. e. usually within about a few orseveral minutes after the oxidizing agent was added and beforeappreciable oxidation of that reaction product occurs, or in otherwords, the ready dyeing solution resulting after the action of theoxidizing agent on the reactant-dye. r

In this specification 3,4-dihydroxyphenylalanine is briefly referred toas dopa, and 3,4-dihydroxyphenylglycine is briefly referred to asdopa-G.

Para-phenylenediamine and derivatives of it, and substances similar toit have been used widely in fur dyeing and to a large extent in hairdyeing, including dyeing growing human hair. However, these substancespossess certain sensitizing or sensitization-provoking reactions andtoxic limitations that provoke distress not only with persons handlingand working with them, or dyeing hair of others with them, butespecially also with many whose hair is dyed with them. Accordingly,certain states and countries prohibit their sale. Others including ourcountry, permittheir sale only under certain restrictions, for example,that their labels bear a warning that mentions their sensitizing orsensitization-provoking reactions and toxic characteristics andrequiresmaking a patch test to determine absence of sensitivity to them beforeusing them.

A significant disadvantage in the use of dopa and dopa-G for dyeing hairis their usual limitation in giving only very light brown and blondeshades, and the need to re-dye to build up color even in this part ofthe range. Then, too, other hair dyes give only a very limited range ofcolor.

United States Patent The reactant-dyes of this invention, are especiallyap- 2,875,769 Patented Mar. 3, 1959 2 1 dark brown and even to very darkblackish-brown In addition, they leave the hair permanently dyed againstrepeated washing and ordinary exposure to light.

The reactant-dyes of the invention, providing these advantageous dyeingfeatures for keratinaceous fibers, especially hair and fur, areobtained, and the method of their preparation is carried out, byallowing the hydroquinone and the dihydroxyphenylalanine, as3,4-dihydroxyphenylalanine, and/or the dihydroxyphenylglycine, as3,4-dihydroxyphenylglycine, to react with one another in suitableproportions in aqueous media and under non acid, and advantageouslyalkaline, conditions, and until the reaction has become substantiallyinactive. By the reaction has become substantially inactive is meantthat stage at which the reaction has slowed down to a rate at which thecolor that developed appears to have discontinued growing any darker.

Practically directly after the joint inclusion of the hydroquinone andeither or both of the amino acids in the aqueous non-acid alkalinemedium, color formation commences and increases in depth until thereaction becomes substantially inactive, that is to say, when thereappears to be no further increase in color depth. That generally occursin from about five to about ten or so minutes, depending on theconcentration of reactants in the alkaline vehicle.

The alkalinity canvary from about pH 8 to about pH 11, and mosteffectively from about pH 9 to about pH 10. Below about pH 8 theresulting hair dyes are undesirable in that the appearance of hair dyed.with them is quite unnatural and rather dull and unattractive.

As to the method of dyeing keratinaceous fibers, for

example, living hair, with the reactant-dyes of the invention, theresulting aqueous reactant-dye solution (whether true or colloidal) ismixed with a suitable quantity of a compatible oxidizing agent (eitherin dry form or as a compatible liquid vehicle or solvent); and theresulting fresh oxidation dyeing solution, for example, is applieddirectly to living hair on the head in the usual manner used bybeauticians or given in directions with home use hair dyes. The latterincludes, for example, parting the hair and applying the fresh oxidationdyeing solution by cotton swab or dauber or other applicator to saturatethe hair close to the scalp and about two inches to each side of thepart line, parting the hair a short distance from the first part andrepeating the saturation of the hair with the dyeing solution, andcontinuing in similar mandant, of the type commonly used for fur dyeingbefore or after they are immersed in the fresh oxidation productobtained from the mixture of reactant-dye composition and oxidizingagent.

For beneficially eifective results, particularly with, al-

though not restricted to, hair (growing or shorn), the

hydroquinone should be used to the extent of at least about ten (10%)percent by weight, or about one-sixth mole of it to one mole of thedihydroxyphenylalanine,

such as 3,4-dihydroxyphenyla1anine, and/or the dihydroxyphenylglycine as3,4-dihydroxyphenylglycine. Much better results are obtained byusing atleast about twenty (20% percent of hydroquinone by weight of the amino 3acid or acids.

Ordinarily,- the quantity of'hydroquinone used can be from under toabout the same as that of the amino acid or acids. Yet, in some casesthe hydroquinone can be used in some excess over it, as when resorcinoland catechol are included with it, as explained below, and then up totwice the amount of the amino acid or acids. In general, the greater theproportion of hydroquinone to the amino acid or acids, the deeper theshade in the dyed fiber. Also, the greater the'concentration, in theaqueous medium, of the reactant-dye (i. e. the reaction product ofthefhydroquinone with the dihydroxyphenylalanine and/ or thedihydroxyphenylglycine), the deeper the resulting shade in the dyeing.

By using either or both of these amino acids, such as dopa and/ordopa-G, and the hydroquinone alone in varying relative proportions toone another for preparation of the reactant-dye compositions, mixingthem with the oxidizing agent, say in solution, and then applying theresulting fresh oxidation product dyeing solution, for example, to hair(growing orvshorn), colors ranging from the palest blonde to the reddestauburn or titian are produced.

For certain variations in color, the hydroquinone can be replaced inpart by an approximately equivalent amount of another polyhydric phenol,such as the trihydric phenol pyrogallol (i. e. pyrogallic acid), or of ac'arboxyl-substituted polyhydric phenol as protocatechuic acid, or quitebeneficially by a quantity of jointly present dihydric' phenols ascatechol and resorcinol.

Some of these color variations, especially in the lighter range, can beobtained by including pyrogallol or protocatechuic acid along with thehydroquinone. The'pr'otoca'techuic acid generally tends to yield alightening of the shade of the same color obtained without its use. -Theuse of pyrogallol generally produces a yellowing of the color obtainedwithout it. Then, by including varying amounts of both resorcinol andcatechol together along with the hydroquinone and thedihydroxyphenylalanine and/or the dihydroxyphenylglycine, Without orwith the pyrogallol or protocatechuic acid, colors ranging from lightbrown to very dark blackish-brown are obtained on the hair.

The specific ultimate color produced in the dyed keratinaceous fiber,such as growing human hair, is influenced not only by the relativeproportions of the various reactants to one another, but also by suchfactors as their respective concentration in the aqueous medium, and thelength of time that the fresh oxidation product dyeing solution remainsin contact with the hair or other fiber during the dyeing step ortreatment. For example, thereactant-dye compositions of individual onesof the specific complete examples below can be separately progressivelydiluted with water even up to nineteen parts of water to one of thereactant-dye compositions, although with not so much dilution of thelighter colors, to .obtainincreasingly lighter colors such as lighterbrowns down to very light blondes.

Any form of the dopa, Whether the synthetic (the racemic form), natural(the laevo-rotatory form), or dextro-rotatory form, and likewise anyform of the dopa-G can be used in preparing the reactant-dyecompositions. Either or both of them can be dissolved independently (atatmospheric temperature) in the alkaline aqueous medium in a suitable,or the required, concentration for the formulation for the particularcolor to be dyed, even up to eighteen, and, if necessary, twenty,percent, or it can be added to the aqueous liquid medium in its requiredconcentration along with the hydroquinone.

The latter can be included also in its required concentration for theparticular formulation, and, depending on the color to be dyed, can bedissolved in asuitable aqueous medium in a concentration even up tothirtyfive (35%) percent, depending on the composition of the aqueousmedium, or as its own aqueous solution up to its solubility limit (orwith the aid of a minimum amount of an inert mutual solvent, e. g.ethanol, beyond its water solubility limit), for the preparation of thereactant-dye composition. At that concentration it represents about fourmoles ofit per mole of the dihydroxyphenylalanine and/or thedihydroxyphenylglycine at the highest concentration mentioned herein ofeither or both of these amino acids.

. Any water-soluble alkalizing agent that will not interfere (i. e. iscompatible) with any necessary reactant used in the formulation, andthat will aid to dissolve any necessary reactant that otherwise isinsufficiently soluble in water, and that will not precipitate theresulting reactant-dye or introduce any possibility of toxicity underthe conditions of use, or injure the scalp or hide or pelt, at itsultimate concentration in the oxidation dyeing solution to be applied tothe living or other hair or other keratinaceous fiber, can be used. Apreliminary test of some selectedalkalizing agent can be made to notevits compatibility with the reactants and inability to precipitate theresultant reactant-dye or to introduce possibility of toxicity or injuryto the skin, pelt, or hide.. Ammonium hydroxide, because of its freedomfrom,

toxicity over a very wide concentration range and its economy, isbeneficial and favored, especially in its commercially commonlyavailable twenty-eight (28%) percent solution.

. However, there can be used in place of, or together with, the ammoniaany other compatible ammonia de-.

rivative alkalizing agent such as a lower alkanolamine as mono-, di-, ortriethanolamine, or a heterocyclic amine as morpholine or pyridine, or alower alkyl monoor di-amine such as monomethylamine, dimethylamine,monoethylamine or diethylamine. Any of these am-- monia derivativealkalizing agents as well as ammonium hydroxide may be broadly referredto as an ammonium alkalizant.

Also as alkalizing agent, any alkaline earth hydroxide,v

for example, calcium hydroxide or magnesium hydroxide (included as analkaline earth), can be used up to the limit of its water-solubility andat any concentration that fails to produce a precipitate with any of theorganic orother reactants. The dissolved alkaline earth hydroxide ispreferred over the alkali metal hydroxides, such as sodium hydroxide orpotassium hydroxide, or. carbonates, such as sodium carbonate andbicarbonate, any of which also can be used so long as its ultimateconcentration in the final dyeing solution is below that.

which might possibly irritate the scalp or skin or injure the hide ofthe fur pelt.

Any selected, compatible alkalizing agent should be used to give a pHgreater than seven and at least about eight and preferably higher andwithin about nine to eleven and most effectively between about nine andabout.

ten and best at around 9.66. However, each of dopa and dopa-G is abutter and can keep the system at.

about pH ten. Even a mixture of alkalizing agents can be used to givethe required pH. Whatever alkalizing agent is used, canbe added to theaqueous medium before, with, or after, the addition of the organicreactants selected for preparing the reactant-dye.

Such other polyhydric phenols, as the pyrogallol,- protocatechuic acid,or catechol with resorcinol, as are to be included in the formulationscan be added to the aqueous medium at the same time as the hydroquinoneand the dihydroxyphenylalanine and/or the dihydroxyphenylglycine.Although if protocatechuic acid is to beused in a relatively highconcentration, it first may need .to be heated alone in water or inpresence of at least some alkalizing agent to go completely intosolution, and then to be added to the other reactants. when all of thereactants and reagents have been dissolved in theaqiieous medium, the pHshould be above seven, effectively to keep all of the reactants insolutioh,

It is beneficial to use initially enough alkali to give a pH that may beeven between about 10.5 and 11. However,

soon after the reaction has been going on for a short time, because ofthe buffering action of the dopa and/ or the dopa-G, the pH will becomeadjusted automatically to about 9.66.

Promptly after some of both of the hydroquinone and thedihydroxyphenylalanine and/ or the dihydroxyphenylglycine has dissolvedin the aqueous medium, reaction between them occurs. Within a fewminutes, and at least usually, within about five to ten minutes, andadvantageously always with stirring, this first reaction (i. e. beforeadding a specific oxidizing agent) is at least substantially complete,that is to say, becomes substantially inactive. By then all of thereactants have gone into solution and reacted together into awater-soluble, or at least colloidally dispersed, reactant-dye product.

This reactant-dye solution is ready now for the subse quent reaction,for it is to be mixed with a suitable compatible oxidizing agent ifdyeing of hair or other fiber is to be done promptly thereafter. In anyevent, this reactant-dye dispersion or product, before being mixed withthe oxidizing agent, is a finished product of the invention, and can beused at any suitable time, soon or later thereafter, on addition of theoxidizing agent, to dye living hair or other keratinaceous fiber.

There can be used any water-soluble oxidizing agent that is compatiblewith this water-soluble, or colloidally water-dispersed, reactant-dyeproduct and that does not introduce into the fresh oxidation product ordyeing solution any possibility of its being toxic to the scalp, orinjurious to the hair or fur or hide or the pelt, at the ultimateconcentration at which it is applied.

Such suitable oxidizing agent is also compatible with the reactant-dyewhen it does not react with the dye to form a water-insolubleprecipitate. Hydrogen peroxide, in any of its commercially commonlyavailable strengths, because of its ready availability and low cost, isfavored. It can be used, for example, as twenty volume or in itstwenty-five volume strength, or even eight and a quarter volume or alsoone hundred volume.

In place of, or together with, the hydrogen peroxide, there can be usedany other compatible oxidizing agent such as any other suitableperoxide, for example, an inorganic peroxide such as an alkali metalperoxide as sodium peroxide, or an organic peroxide as urea peroxide, orother water-soluble inorganic oxidizing agent as an alkali metalchlorate, bromate, or perborate such as sodium or potassium chlorate,bromate or perborate. Any of the foregoing, or compatible mixtures ofthem, can be used in preparing the dyeing solutions for dyeing livehair. In wool or fur dyeing any of them, or others, can be used.

For use in dyeing living hair or other keratinaceous fiber, thereactant-dye product of the invention is mixed with a quantity of theoxidizing agent, Whether liquid or solid, suflicient to give aconvenient concentration in relation to the concentration of thereactant-dye in its solution and the concentration desired in theoxidized dye solution as it is to be applied to the hair or fur or otherkeratinaceous fiber. For example, hydrogen peroxide (twenty volume) canbe mixed with the reactantdye solution usually in an amount of fromabout one quarter to one-half of, or up to equal parts or even twice,the volume of the reactant-dye solution. The solid oxidizing agents canbe granulated or powdered and thus added to, and dissolved in, thereactant-dye solution, although in some cases it is advantageous todissolve such oxidizing agent separately in Water.

The selection and quantity of the oxidizing agent will depend on thecondition of the fiber to be dyed and the color to be developed in thedyeing rate. In some cases, a preliminary test on a trial lock or switchof hair or skcin or swatch of wool or patch of fur may be necessary as aguide.

The reactant-dye dispersion and the oxidizing agent,

in solution or solid, are m ed together uniformly to give what can bereferred to as the oxidation dye or dyeing solution, for application tothe hair. There can be included a suitable compatible wetting agent orother surfactant. It is best that the oxidation dyeing solution beapplied to the hair or other fiber promptly after the reactant-dyesolution and the oxidizing agent have been mixed, and preferably notmore than about ten minutes or so after mixing the reactant-dyedispersion and the oxidizing agent.

The oxidation dyeing solution then can be applied tow the hair or otherfiber in known manner. The hair or other fiber is kept in contact withthe dyeing solution for a sufficient time for the desired color andshade of it to develop from its contact of the fiber with the dye. Formost cases, as so far noted, the dyeing time can be from about fifteento about seventy-five minutes, and often from about a half hour to aboutan hour. The dyeing reaction between the fiber and the oxidation dyeingsolution is then terminated by shampooing and/or rinsing the hair orother fiber to remove the exhausted and any excess dyeing solution.

The reactant-dye compositions and oxidation dyeing solutions, andmethods, of the invention are illustrated by, but not restricted to, thefollowing examples which include also quantities of an oxidizing agentused relative to the reactant-dye solution produced:

Example 1.Very pale blonde on wool: one gram of3,4-dihydroxyphenylalanine and one-half gram of hydroquinone weredissolved in twenty-five milliliters of water to which was added twomilliliters of twenty-eight per cent ammonium hydroxide solution. Withina few minutes there resulted a clear, light brown reactant-dye solution.To make the dyeing solution, five milliliters of twenty volume hydrogenperoxide were added to fifteen milliliters of this light brown solution.A swatch of unbleached wool was rinsed in the twenty milliliters of thisoxidation dyeing solution for fifteen minutes and then was removed andwashed, and appeared as a very pale blonde dyed product. This colorremained permanent, without running, after repeated washings in waterwith shampoo. The color also remained permanent after extended exposureto sunlight.

Example 2.Very pale blonde on grey hair: two and one-half grams of3,4-dihydroxyphenylalanine and onequarter gram each of hydroquinone andpyrogallol were dissolved in fifty milliliters of water to which wasadded four milliliters of twenty-eight percent ammonium hydroxidesolution. Within a few minutes there resulted a clear, light brownreactiondye solution. To this solution there was added an equal volumeof twenty volume hydrogen peroxide, yielding inseveral minutes a lightbrown dyeing solution. This dyeing solution was applied to hair in knownmanner and allowed to remain for forty minutes dyeing time, after whichthe dyeing reaction was stopped by thorough shampoo and water rinse.About one and one-half ounces of dyeing solution was needed. The colordid not change on repeated washings in water with shampoo. The sameresults were obtained on applying this fresh oxidation dyeing solutionto living hair' by the method described in the paragraph beginning online 32, column 2, above.

Example 3.-Champagne color on grey hair: two grams of3,4-dihydroxyphenylalanine, one-half gram of hydroquinone, two grams ofresorcinol and one gram of catechol were dissolved in fifty milliliters.of water to which five milliliters of twenty-eight percent ammoniumhydroxide were added. After five minutes, there was added to thisreactant-dyesolution one-half of its volume of twenty volume hydrogenperoxide. The resulting oxidation dye solution was applied to grey hairin known manner for thirty-five minutes dyeing time and then removed bya thorough shampoo and water rinse, leaving a good uniform, fastchampagne color which was not removed by repeated washings.

estates Example 4; Blondeon grey hair: two grams each of3,4wdihydroxyphenylalanine and hydroquinone were dissolved in thirtymilliliters of water to which three and one-'half'milliliters oftwenty-eight percent ammonium hydroxide were added. After five minutes,there was added to this reactant-dye solution an equal volume of twenty.volume hydrogen peroxide. The resulting oxidation dyeing solution wasapplied to grey hair in known manner for forty minutes dyeing time. Thenthe dyeing reaction was stopped by a thorough shampoo and water rinse..The hair was dyed a good, uniform blonde which Was not changed byrepeated washings.

Example 5 .Red maize on grey hair: two grams of 3,4-dihydroxyphenylalanine and three grams of hydroquinone were dissolvedwith vigorous stirring in twenty-five milliliters of water, to whichfour milliliters of twenty-eight percent ammonium hydroxide were added.After ten minutes, an equal volume of twenty volume hydrogen peroxidewas added. The resulting oxidation dye solution was applied to grey hairin known manner for forty minutes dyeing time and then removed by athorough shampoo and water rinse. The hair was dyed a uniform red maizecolor which withstood repeated Water washings.

Example 6.-Pale henna on grey hair: two grams of3,4-dihydroxyphenylalanine, four grams of hydroquinone and fiveone-hundredths of a gram of pyrogallol were dissolved with vigorousstirring in twenty-five milliliters of,

water to which four milliliters of twenty-eight percent ammoniumhydroxide had been added. After ten minutes,

- an equal volume of twenty volume hydrogen peroxide was added. Theresulting oxidation dye solution was applied to grey hair in knownmanner and maintained for a forty minute dyeing time and then removed bya thorough shampoo and water rinse. The hair was dyed a uniform palehenna and showed no loss in color on repeated water washings.

Example 7.-Reddish brown on grey hair: four grams of3,4-dihydroxyphenylalanine and three grams of hydroquinone weredissolved in sixty milliliters of water to which five milliliters oftwenty-eight percent ammonium hydroxide had been added, and withvigorous stirring until solution was complete. Then there was addedonequarter the volume of twenty volume hydrogen peroxide and thesolution uniformly mixed. The resulting oxidation dye solution was thenapplied to grey hair in known manner and maintained for a forty minutedyeingtime and then removed by a thorough shampoo and water rinse. Therinsed hair was dyed a uniform, beautiful reddish brown and showed noloss in color during repeated water washings.

Example 8.Medium brown on grey hair: six grams of3,4-dihydroxyphenylalanine, three and one-half grams of hydroquinone,six grams of resorcinol and one gram of catechol were vigorously stirredin forty milliliters of water to which was added fourteen milliliters oftwentyeight percent ammonium hydroxide, until solution was complete.Then for every twenty milliliters of the solution there was added fivemilliliters of twenty volume hydrogen peroxide. The resulting oxidationdye solution was then applied to grey hair in known manner and allowedto remain in contact with the hair for fiftyfive minutes dyeing time,after which the unconsumed dyeing solution was removed by thoroughlywashing with water and shampoo. The rinsed hair was dyed a beautifulmedium brown.

Example 9.Rusty auburn on grey hair: four grams of3,4-dihydroxyphenylalanine and three grams of hydroquinone werevigorously stirred in forty milliliters of water to which had been addedfive milliliters of twentyeight percent ammonium hydroxide, untilsolution was complete. Then there was uniformly stirred in one-half th evolume of twenty volume hydrogen peroxide. The resulting oxidation dyesolution was then applied to grey hair in known manner and allowed toremain in contact with it for a arra -five minutedyeing time. Then theadded twelve and one-half milliliters of twenty volume hydrogen peroxideto give a uniform oxidation dyeing solution. The latter was then appliedto grey hair in known manner and allowed to remain in contact with itfor a seventy-five minute dyeing time. solution was then removed bythorough shampoo and rinsing with water, leaving the hair dyed a darkbrown.

In each ofthe foregoing Examples 1 through 10, replacement of the dopaby respectively the same quantity of dopa-G gives the same dyeingresults on the specific fiber and human hair (shown or living) used inthe individual examples. Accordingly, without unduly extending thisspecification by repeating each such separate dopa-G example in full,Examples 1 through 10 with their separate amounts of dopa replacedrespectively by the same amount of dopa-G are incorporated herein bythis reference as if each of them as so modified were recited in fullherein.

. The various respective fiber (i. e. hair) dyeings obtaiued separatelyin each of the foregoing Examples 2 through 10, and also in theirduplicates with the dopa replaced by dopa-G, were obtained on growingliving hair by the method of application of the fresh oxidation dyeingsolution described in the paragraph beginning on line 32, column 2,above.

The invention thus includes the method of dyeing growing hair withsignificant fastness to light and water which-comprises subjecting suchhair, for a time sufficient for the desired color and shade to developon it,

to the action of an oxidation dyeing solution prepared by mixingtogether uniformly an aqueous alkaline, reactant-dye colored compositionand an oxidizing agent compatible with the compositions constituents andthe hair under the dyeing conditions, for example, hydrogen peroxide,and in a quantity sufficient to yield a suitable oxidizer concentrationin relation to the reactant-dye concentration in its solution and theconcentration in the fresh oxidation dyeing solution for the desiredcolor and.

shade to be developed on the hair. After the desired color and shade ofit is developed on the hair, the spent and any excess dyeing solution isremoved from the hair, for example, by shampooing.

In Examples 1 through 10, the dopa can be replaced by respectively thesame quantity .of a suitable isomer of it. Likewise, the proportions ofthe various ingredients can be varied to give desired variations incolor and their intensities, in the manner as above indicated to bepossible. Then also it is possible to replace any polyhydroxy phenolused singly to replace a minor part of the hydroquinone by some otherphenol having, say, at least three hydroxyl groups, such astetrahydroxyquinone.

Thus, for instance, by including in Example 1 also one one-hundredthgram of tetrahydroxyquinone, the fiber is dyeda light brown. Thepyrogallol can be used in an amount as small as about one-tenth percent,and at times less, of the hydroquinone up to about equal to it and evengreater than it, say two, three, and four times as much. Thetetrahydroxyquinone likewise can be used within the limit of itssolubility in the aqueous alkaline medium. There can be used similarly1,2,4-trihydroxybenzene (i. e. hydroxyquinol).

Likewise, protocatechuic acid can replace the hydroquinone in part.Thus, by the procedure used in the various examples, but. with 1 gram,of 3,4-dihydroxyphenylalanine, one-half gram of hydroquino'ne, and 2grams of ,protocatechuic acid, and three millilitersiof The dyeing ofwater, after solution was complete, a suitablereaction: dye resulted. Anoxidation dyeing solution of fifteen parts of this reaction'dye solutionwith two parts of twenty volume hydrogen peroxide produced on grey hairfrom a good medium brown blonde to a good pale brown blonde dye. Usingtwo grams of 3,4-dihydroxyphenylalanlne, five grams of hydroquinone, sixgrams of protocatechuic acid, six milliliters of the ammonium hydroxidesolution with one hundred milliliters of water, and two parts of thecolor solution to one of the twenty volume hydrogen peroxide, grey hairwas dyed a good medium brown.

Reacting one gram of dopa and one gram of protocatechuic acid in fiftymilliliters of water and three milliliters of 28% ammonium hydroxide,and using one part of the resulting reactant-dye solution to one-halfpart of the twenty volume hydrogen peroxide, grey hair was dyed a palestraw with good tone.

Instead of using either thedopa and/or the dopa-G or the protocatechuicacid in its respective free acid form, the equivalent quantity of awater-soluble salt of it can be used, for example, an alkali metal saltsuch as the sodium or potassium salt, or the ammonium salt, or a loweralkanolamine salt of it such as a mono-, dior triethanolamine'salt. Onsolution in water, such salt can produce a pH above seven and evenaround eight, and then require addition of only a smaller amount of thealkalizing agent to give the desired alkaline conditions for thereaction to produce the reactant-dye. Accordingly, the reference to adihydroxyphenylalanine and specifically to 3,4-dihydroxyphenylalanine,or a dihydroxyphenylglycine and specifically to3,4-dihydroxyphenylglycine or to 3,5-dihydroxyphenylglycine, or toprotocatechuic acid, in the appended claims is to be construed asinvolving any of these salts as equivalents of the respectivelycorresponding free acid.

Either a suitable wetting agent or suspending agent can be included inthe compositions of any of the examples, but neither of these isessential to the preparation of the reactant-dye. A compatible wettingagent serves ordinarily to facilitate penetration of the reactant-dye. Acompatible suspending agent serves to reduce flow or drainage from thehair. Either or both can be any'compatible wetting agent or suspendingagent respectively, that is innocuous in its final concentration in thefresh oxidation product dyeing solution. Either of them can be includedafter the reactant-dye has been produced.

The specific resulting color produced in the dyed hair or other fiber isinfluenced by the relative proportions of the various reactants to oneanother, their respective concentrations in the aqueous media, and thetime that the fresh oxidation product dyeing solution remains in contactwith the hair or other fibers.

The ammonium hydroxide can be replaced in whole or in part by any othercompatible ammonium alkalizant or other alkalizing agent innocuous tothe scalp or fur or pelt at its final concentration in the ultimatefresh oxidation product dyeing solution. So also while hydrogen peroxideis advantageous as the oxidizing agent, it can be replaced in whole orpart by any other compatible oxidizing agent that is innocuous at itsfinal concentration in the ultimate fresh oxidation dyeing solution.

Instead of using distilled water in preparing the reactant-dye products,de-ionized water can be used. Either distilled or deionized water ispreferred in preparing the reactant-dye compositions in market packagesto stand up under shelf life. Ordinarily, average good quality citywater can be suitable where the reactant-dye compositions are to be usedin preparing a dye-bath for fur, wool, or other loose keratinaceousfibers.

The reactant-dyes of the invention are water-dispersable in the usualgeneric sense as embracing true stable homogeneous colloidal solutionsof them in such aqueous medium. Thus, the aqueous-medium includes theaqueous alkaline medium resulting from the alkalizing agent used eithermerely to provide the alkalinity or to enhance the dissolution of someorganic reactant in the water. It includes also any aqueous mediumcontaining, for example, a sufficient amount of any oxygenated loweraliphatic mono or dihydric alcohol employed as a common solvent toenhance the solution of some organic reactant, for example, any loweraliphatic alcohol as ethanol, methanol, propanol or iso-propanol, orlower aliphatic glycol such as propylene glycol and the like.

The reactant-dye of any of the various illustrative examples, as well asany other produced according to the invention, can be obtained in thedry state by removing the aqueous vehicle by a procedure that avoidsoxidation or decomposition of, or any other deleterious effect on, it.Thus, for example, the reactant-dye can be removed from the aqueousvehicle in which it is dispersed (either in true solution-or colloidaldispersion) by lyophilization. Accordingly, the aqueous dispersion ofthe reactant-dye can be frozen and in the frozen state subjected to highvacuum to sublime away the frozen vehicle and leave behind the dryreactant-dye.

Alternatively, the dispersion of reactant-dye can be spray dried underconditions to avoid deleterious change.

in it, for example, by spraying it into an inert atmosphere, forexample, carbon dioxide or nitrogen, or air mixed with either of themsufficiently to reduce its oxygen content to a harmless point, with orwithout using a spraying medium inert to the reactant-dye. Such mediumcan be a gas or mixture of gases as just mentioned for the inertatmosphere.

Such dried reactant-dye then can be put up either as a free runningpowder in bottles or powder papers (such as used for pharmaceuticals) oreven can be tabletted. For tablets, it can be helpful and desirable insome cases to incorporate a suitable inert binder to give addedphysical.

strength to the tablets, or ingredients to enhance their disintegrationwhen placed in Water. In packaging the reactant-dye in any of these dryforms, it is beneficial to have the container filled sufiiciently toleave in it as little air as possible and to close it tightly to avoid,while not in use, replacement of the air already in the package.

Advantageously, such powder paper or tablet can contain enoughreactant-dye for a complete single dye treatment, for example, whenprepared for dyeing hair on the head. When to be used, the reactant-dyeeither can be dissolved or otherwise dispersed in a separate suitablequantity of water and then mixed with the required amount of oxidizingagent solution, or it can be added directly to, and dissolved in, wateralready containing the required amount of the oxidizing agent.

The dry reactant-dye powder can be used for permanent dyeing by stirringa given quantity into a stated volume of water having dissolved in itsufficient of any of the alkalizing agents described above to give theresulting solution a pH above about eight and in the range alreadystated for the reactant-dye solution before it is mixed with theoxidizing agent. Alternatively, the dry reactant-dye powder can be mixedwith a powdered, water-soluble, preferably non-hygroscopic, solidalkali, for example, ammonium carbonate, innocuous in its finalconcentration in the final dyeing solution, and in such ratio that whena given quantity of the dry mixture is stirred into a prescribed volumeof Water, the pH of the resulting solution is within the range shownhereinabove.

In general, the various oxidation dyeing solutions containing any.of thevarious reactantdyes described can be applied with good results to hairwhether or not it had been previously washed and are fast to washing andsunlight.

While the invention has been explained in detail in relation to certainspecific embodiments of it, various seas-as substitutions andmodifications can be made in any of them within the scope of theappended-claims which are intended also to cover equivalents of any ofthe various specific examples.

.This application is a continuation-in-part of our copending applicationSerial No. 350,756 filed April 23, 1953, and now abandoned.

What is claimed is:

l. A colored composition of matter comprising a waterdispersablereactant-dye useful in the dyeing of keratinaceous fibres withsignificant fastness to light and water, which dye results from the,reaction, in an aqueous medium under alkaline conditions produced by acompatible water-soluble alkalizing agent that dissolves any of thereactants insufficiently soluble under the conditions and avoidsformation of a precipitate with any of the reaction products under thereaction conditions, between hydroquinone and at least one amino acidmember of the class consisting of a dihydroxyphenylalanine having aformula (HO) C H CH CH(NH )COOH and a dihydroxyphenyh glycine having theformula .(HO) C H CH(NH )COOH, until the reaction is substantiallycomplete, and wherein the hydroquinone is from about ten to about twohundred percent by weight of the amino acid used.

, 2. Acomposition comprising a reactant-dye as claimed in claim 1,wherein the hydroquinone is replaced in part by at least one polyhydricphenol member of the class consisting of pyrogallol and protocatechuicacid, and in the proportions of from a minor part of the hydroquinone toseveral times the remaining quantity of it.

3. A composition comprising a reactant-dye as claimed in claim 2,wherein the hydroquinone is replaced in a minor part by pyrogallol.

4. A composition comprising a reactant-dye as claimed in claim 1,wherein the hydroquinone is accompanied by at least one other polyhydricphenol substance from the class consisting of (a) tetrahydroxyquinone,(b) hydroxyquinol, and (c) resorcinol and catechol jointly, and in theproportions of from a minor part of the hydroquinone to several timesthe remaining quantity of it.

5. A composition comprising a reactant-dye as claimed in claim 4,wherein the hydroquinone is accompanied by resorcinol and catechol.

6. A composition comprising a reactant-dye as claimed in claim 5,wherein the weight of the dihydrophenylalanine is exceeded by the jointweight of the hydroquinone and resorcinol and catechol.

7. A composition comprising a reactant-dye as claimed in claim 6,wherein the resorcinol and catechol jointly exceed the weight of thehydroquinone, and the catechol weight is under, and at least about tenpercent of, that of the resorcinol.

8. .An aqueous alkaline colored composition comprising awater-dispersable reactant-dye useful in the dyeing of keratinaceousfibers with significant fastness to light and water, which dye resultsfrom the reaction, in an aqueous medium under alkaline conditionsproduced by a compatible water-soluble alkalizing agent that dissolvesany of the reactants insufiiciently soluble under the conditions andavoids formation of a precipitate with any of the reaction productsunder the reaction conditions, between 3,4-dihydroxyphenylalanine andhydroquinone until the reaction is substantially complete, and whereinthe hydroquinone was from about ten to about two hundred percent byweight of the dihydroxyphenylalanine; and having a pH of from abouteight to under about eleven.

9. An aqueous alkaline colored composition comprising awater-dispersable reactant-dye useful in the dyeing of keratinaceousfibers with significant fastness to light and water, which dye resultsfrom'the reaction, in an aqueous medium under alkaline conditionsproduced by a compatible water-soluble alkalizing agent that dissolvesany of the reactants insufficiently soluble under the conditions andavoids formation of a precipitate with any of aceousfibers under thedyeing conditions, and

the reaction products under the reaction conditions, between3,4-dihydroxyphenylglycine and hydroquinone until the reaction issubstantially complete, and wherein the hydroquinone was from about tento about two hundred percent by weight of the dihydroxyphenylglycine andhavlng a pH of from about eight to under about eleven.

10. An aqueous alkaline composition as claimed in claim 9, wherein thehydroquinone is replaced in a minor part by a member of the classconsisting of pyrogallol and protocatechuic acid.

ll. An aqueous alkaline composition as claimed'in claim 9, wherein thehydroquinone is accompanied by at least one other polyhydric substancefrom the class conslstmg of (a) tetrahydroxyquinone, (b) hydroxyquinol,and (0) resorcinol and catechol jointly, and in the proportion of from aminor part of the hydroquinone to several times the remaining quantityof it.

1 2. An aqueous alkaline composition as claimed in claim 11, wherein theweight of the dihydroxyphenylglycine is exceeded by the joint weight ofthe hydroquinone and the resorcinol and catechol, and the resorcinol andcatechol jointly exceed the weight of the hydroquinone, and the catecholweight is under, and at least about ten percent of, that of theresorcinol.

l3 The method of preparing a colored, aqueous composition as claimed inclaim 11, which comprises dissolv ing in water3,4-dihydroxyphenylglycine to a concentratron of from about a few toabout twenty percent, hydro- .quinone in an amount from about ten toabout two hundred percent by weight of the dihydroxyphenylglycine,

and, to an extent to leave the resulting composition alkaline and at apH under about eleven, a water-soluble alkalizing agent that dissolvesany of the reactants instilliclently soluble under the conditions andavoids formation of a precipitate with any of the reaction productsunder the reaction conditions; and agitating the water until all of thereactants have gone into solution.

l4. The method of preparing a colored composition as claimed in claim13, wherein a minor part of the hydro qu none is replaced by apolyhydric phenol from the class consisting of pyrogallol andprotocatechuic acid.

15. The method of preparing a colored composition as claimed in claim13, wherein the hydroquinone'is acconi:

panied by resorcinol and catechol and their joint weight exceeds that ofthe hydroquinone and the resorcinol exceeds the weight of catechol.

16. The method of dyeing keratinaceous fibers, which comprisessubjecting them, for a time sufiicient for the desired color and shadeto develop on them, to the actron of an oxidation dyeing solutionprepared by mixing together uniformly an aqueous alkaline. reactant-dyecolored composition and an oxidizing agent compatible with theconstituentsof said composition and the keratinin a quantity suificientto yield a suitable concentration of it in relation to the reactant-dyeconcentration in its solution and the concentration in the oxidationdyeing solution for the color and shade to be developed on thekeratinaceons fiber; the aqueous colored composition comprising areactant-dye for dyeing the keratinaceous fibers with significantfastness to light and water, which dye results from the reaction, in anaqueous medium under alkaline conditions, produced by a compatiblewatersoluble alkalizing agent that dissolves any of the reactantsinsufficiently soluble under the conditions and avoids formation of aprecipitate with any of the reaction products under the reactionconditions, between hydro-- quinone and at least one amino acid memberof the class consisting of a dihydroxyphenylalanine have the formula(HO) C H CH CH(NH )COOH and a dihydroxyphenylglycine have the formula(HO) C H CH(NH )COOH; withe the hydroquinone being from about ten toabout two hundred percent :of the weight of the .amino acid content; andremoving the spent and any excess dyeing solution from the fibers whenthe desired color and shade has been developed on them.

17. The method of dyeing keratinaceous fibers as claimed in claim 16,wherein the keratinaceous fiber is growing hair, and the oxidizing agentis hydrogen peroxide, and ammonium hydroxide is the agent for providingthe alkaline conditions for the preparation of the reaction-dye, and aminor part of the hydroquinone is replaced by pyrogallol.

18. The method of dyeing keratinaceous fibers as claimed in claim 16,wherein the keratinaceous fiber is growing hair, and the oxidizing agentis hydrogen peroxide, and ammonium hydroxide is the agent for providingthe alkaline conditions for the preparation of the reaction-dye, and thehydroquinone is accompanied by resorcinol and catechol, and the jointweight of the hydroquinone, resorcinol and catechol exceeds that of thedihydroxyphenylalanine, and the catechol weight isunder, and at leastten percent of, the weight of the resorcinol.

19. The method of dyeing keratinaceous fibers as claimed in claim 16,wherein the keratinaceous fiber is growing hair, and the oxidizing agentis hydrogen peroxide, and ammonium hydroxide is the agent for providingthe alkaline conditions for the preparation of the reaction-dye, and thehydroquinone is accompanied by resorcinol and catechol, and the jointweight of the hydroquinone, resorcinol and catechol exceeds that of theamino acid content, and the catechol weight is under, and at least tenpercent of, the Weight of the resorcinol.

References Cited in the file of this patent UNITED STATES PATENTS2,001,992 Wagner May 21, 1935 2,042,698 Basch June 2, 1936 2,162,458Lehmann June 13, 1939 2,539,202 Peck Jan. 23, 1951 FOREIGN PATENTS10,856 France Sept. 4, 1909 (Addition to No. 391,465) 17,982 GreatBritain 1913 1,024 Great Britain 1915 20,793 Great Britain 1913 487,279Great Britain June 16, 1938

1. A COLOURED COMPOSITION OF MATTER COMPRISING A WATERDISPERSABLERACTAN-DYE USEFUL IN THE DYEING OF KERTINACEOUS FIBRES WITH SINGNIFICANTFASTNESS TO LIGHT AND WATER, WHICH DYE RESULTS FROM THE REACTION. IN ANAQUEOUS MEDIUN UNDER ALKALINE CONDITIONS PRODUCTED BY A COMPATIBLEWATER-SOLUBLE ALKALIZING AGENT THAT DISSOLVES ANY OF THE REACTANTSINSUFFICIENTLY SOLUBLE UNDER THE CONDITIONS AND AVOIDS FORMATION OF APRECIPITATE WITH ANY OF THE REACTION QUINONE AND AT LEAST ONE AMINO ACIDMEMBER OF THE CLASS QUINONE AND AT LEAST ONE AMINO ACID MEMBER OF THECLASS CONSISTING OF A DIHYDROXYPHENYLALANINE HAVING A FORMULA(HO)2C6H3CH2CH(NH2)COOH AND A DIHYDROXYPHENYLGLYCINE HAVING THE FORMULA(HO)2C6H3CH(NH2)COOH, UNTIL THE REACTION IS SUBSTANTIALLY COMPLETE, ANDWHEREIN THE HYDROQUINONE IS FROM ABOUT TWO HUNDRED PERCENT BY WEIGHT OFTHE AMINO USED.